18 Fuel Properties Determined in 3 Minutes by Raman Spectroscopy

Providing Chemical Information When & Where You Need It

Carl Brouillette, Frank Inscore,

Michael Donahue, Stuart Farquharson, and

Wayne Smith

www.rta.biz

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Need: Fuel, the most important supply

• The US Military consumes 300,000 gallons of fuel each day in Afghanistan.

• There are only 4 ground supply routes (e.g. Khyber Pass).

• Convoys are easy targets for road side bombs.

• 1 in 5 US casualties in Afghanistan is the result of protecting fuel and water convoys.

• The use of local fuel would reduce human

casualties costs, and increase combat unit mobility during operations.

• But local fuel must be free of adulterants

(sabotage) or contaminants and meet Critical Fuel Property Values.

Petroleum Quality Analysis System-Enhanced (PQAS-E)

• 16 Standard Tests • 2-3 hours (1-2 days for sample delivery) • BUT, can’t do adulterants or biofuels • Needs HVAC & Generator • $1.2 Million

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Current Capability

Concept Overview: Portable Fuel Analyzer Operation: • No Sample Preparation • 3-Minute Measurement • Portable (25 pounds) • Battery Powered (+AC adapter) • Rugged • Wireless Comm.

Analysis: • acidity • alcohols • aromatics • ether • olefins • saturates • sulfur

• cetane index • cloud point • density • distillation values • flash point • freeze point • lubricity • net heat • octane rating • pour point • viscosity

• Broad Temp Range

Red = critical properties 4

• Spill Resistant

Providing Chemical Information When & Where You Need It

The disadvantages usual decide which spectroscopy to use.

Providing Chemical Information When & Where You Need It

Selecting a Technology: Vibrational Spectroscopy

Providing Chemical Information When & Where You Need It

Selecting a Technology:

Vibrational Spectroscopy

Raman: numerous peaks

Infrared: few peaks

NIR: few, broad, overlapping peaks

• •

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Raman Spectra of Basic Fuels

Providing Chemical Information When & Where You Need It

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No peaks!

No unique peaks!

Raman: Every spectrum is different

NIR: peaks are not distinct, often not unique, and sometimes no peaks at all

General Unknowns: Raman vs Near-Infrared

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Raman: different fuels produce different spectra NIR: all fuels look alike

Fuels: Raman vs Near-Infrared

All Other Raman Analyzers 785 nm

Laser Excitation

RTA 1064 nm

Laser Excitation

Diesel Fuel

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785 nm excitation generates fluorescence and does not allow analysis.

RTA Advantage: No Fluorescence

Providing Chemical Information When & Where You Need It

5.0

Raman Shift, cm-11700700 800 900 1000 1100 1200 1300 1400 1500 1600

11 Providing Chemical Information When & Where You Need It

Diesel 2 (±-8 cm-1)

Dispersive Raman Analyzers change wavenumber response with temperature: 2 cm-1 shift produces wrong values. 8 cm-1 shift produces wrong decisions!

RTA Advantage: No Wavenumber Shift

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RTA’s Military Grade Portable Fuel Analyzer

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Validation of Ruggedness: Composite Wheeled Vehicle Vibration: 810F

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Validation of Ruggedness: 26 Drop Tests: 810F

How it Works: Basis for Correlations Raman Measures Chemical Composition, Chemical Composition Dictates Properties

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Chemical Composition

Physical Properties

Raman Spectra

Providing Chemical Information When & Where You Need It

• •

Naphthalene, d=1.02 g/ml Cetane, d =0.77 g/ml

Wavenumbers (∆cm-1)

Fingerprint Region CH Region

Naphthene Stretch

Alkane CH2 Stretch

Ram

an In

tens

ity

Reg

ress

ion

Coe

ffici

ent 6

3

0

-3

-6

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Density: Raman Spectral Correlations

Providing Chemical Information When & Where You Need It

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Density: Raman Spectral Correlations

32 Jet Samples

Pred

icte

d D

ensi

ty (g

/cm

3)

Measured Density (g/cm3) All fuel types (over 800 fuel samples)

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Correlation = 0.985 Raman Error = ±0.004 ASTM = ±0.0008 ALL FUELS

Jets

Diesel 2

Measured Value

Correlated Value

Density: ASTM-Raman Correlations

Providing Chemical Information When & Where You Need It

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Sulfur: ASTM-Raman Correlations

Correlation = 0.95 Raman Error = ±0.11 168 Diesels

Correlation = 0.96 Raman Error = ±0.01 75 ULSD

Accurate ASTM data = smaller Raman error

Providing Chemical Information When & Where You Need It

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User Interface: 17 Properties

Providing Chemical Information When & Where You Need It

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or

Military

User Interface: Designed for Customer Commercial

Providing Chemical Information When & Where You Need It

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Software Architecture: Decision Tree

Is it a fuel? Is it D - 2, JP - 5 or JP - 8? No

ID contaminant Yes No

Yes

Identify liquid ID fuel type

Is it marginal?

Is it contaminated? No

Can I use as D - 2, JP - 5 or JP - 8?

Yes

Yes YES

Provide critical properties

No

NO No

Yes

Providing Chemical Information When & Where You Need It

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User Interface: More Properties

Providing Chemical Information When & Where You Need It

Diesel-2

Biodiesel-100

Sasol-Jet

Hydraulic oil

Gasoline

Isopropyl Alcohol

Raman NIR

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User Interface: Properties

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Diesel-2 JP-8 or JP-5

User Interface: More Properties

Providing Chemical Information When & Where You Need It

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15 Unknown Samples

All fuels correctly identified

All properties Correct within error

Two fuels correctly identified

as marginal

Providing Chemical Information When & Where You Need It

Validation of Analysis: SwRI Results

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Repeatability: “we found the measurement repeatability of the PFA to be very good, and in many cases, better than the ASTM repeatability.” Accuracy: “the accuracy of the PFA was in good agreement with the ASTM measurements. The exceptions were primarily in the estimation of density and viscosity, for which ASTM methods give extreme accuracy.” Hot & Cold: “It was also found that the cold and hot temperature measurements provided virtually the same repeatability and accuracy.” Go /No-Go: “In terms of go / no-go determinations, the PFA correctly rejected the five other fluids. The PFA also correctly identified the diesel and jet fuels by type (diesel, JP-5, or JP-8)” Ease-of-use: “the PFA was very easy to use and each sample was measured in 2-3 minutes, whereas the battery of ASTM measurements to determine the same properties requires as much as 2-3 hours. In summary, for its intended use, the PFA provided sufficient repeatable and accurate determination of fuel properties to provide a go / no-go determination for use of unknown fuels over the measured temperature range and would provide the U.S. Marines with greater flexibility and more control of tactical and emergency situations.

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Summary The Portable Fuel Analyzer can Automatically Identify:

Every common fuel: • 7 Critical Properties for Diesels and Jets • 10 Additional Properties

Numerous Other Chemicals as Unknowns • Over 50 common petroleum products (lubricants, etc.) • Every common solvent (including water) • Over 500 general chemicals (including explosives) • Chemical contaminants at < 1% • Petroleum contaminants at < 5%

• Biodiesel at < 2%

Providing Chemical Information When & Where You Need It

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Providing Chemical Information When & Where You Need It

Keeping the Military Moving

RamanPro In-Process, Continuous Analysis! No Sample Preparation!

• Fluorescence Free Raman • Analyzer Always Calibrated • Universal Interface • Industry Hardened

Real-Time Biodiesel BlendingAnalysis

Providing Chemical Information When & Where You Need It

• Percent Biodiesel • Cetane Index • Cloud Point • Density • Distillation values • Flash point • Sulfur • Viscosity

B100 B50 B20 B5

Analysis that can be done:

Raman Calibration Curve Precision ±1.5%

Real-Time Synthetic Fuel Analysis

Diesel 2 Sasol (FT) Diesel B100 Biodiesel

Petroleum, Synthetic, and Blends can be identified. Providing Chemical Information When & Where You Need It

Portable Fuel Analyzer Fuel Properties in 3 minutes!

No Sample Preparation!

• Cloud Pt • Pour Pt • Flash Pt • Freeze Pt • Distill Pts

• Cetane • Density • Lubricity • Net Heat • Viscosity

• Acid # • Aromatics • Olefins • Saturates • Sulfur • Water

RamanPro In-Process, Continuous Analysis! No Sample Preparation!

• Fluorescence Free Raman • Analyzer Always Calibrated • Universal Interface • Industry Hardened